KR20170034757A - Preparation method of polyalkylene carbonate - Google Patents

Abstract

The present invention relates to a production method of polyalkylene carbonate and, more specifically, to a production method of polyalkylene carbonate, which uses a solution polymerization of an epoxide compound and carbon dioxide. In addition, the method can effectively produce polyalkylene carbonate having molecular weight of various grades without additionally injecting a separate molecular weight control agent (chain transfer agent) by controlling the water content contained in a reactant to an optimum range.

Description

PREPARATION METHOD OF POLYALKYLENE CARBONATE < RTI ID = 0.0 >

The present invention relates to a method for efficiently producing a polyalkylene carbonate having various molecular weights without adding a separate chain transfer agent by adjusting the moisture content of the reactants and the solvent to an optimum range .

Polyalkylene carbonate is a non-crystalline transparent resin, unlike an aromatic polycarbonate which is a similar type of engineering plastic, exhibits biodegradability and is thermally decomposable at a low temperature, and has the advantage of being completely decomposed into carbon dioxide and water and having no carbon residue Have.

Therefore, many researchers have made various research and development for producing polyalkylene carbonate from epoxy compounds and carbon dioxide. However, at present, polyalkylene carbonates copolymerized with an organometallic catalyst exhibit a high molecular weight distribution, so that it is difficult to manufacture and process, resulting in poor usability and a very low production yield due to high viscosity. In particular, there is a need to lower molecular weight for commercial commercialization, and production of various grades of molecular weight products has been required. However, the change in molecular weight due to polymerization parameters (temperature, pressure) that are relatively easy to control is not clear.

Therefore, it is necessary to study a mechanism for lowering or controlling the molecular weight of the polyalkylene carbonate to an appropriate level, and at the same time, it should have a selectivity higher than a certain level. When the additional material is added to adjust the molecular weight, the additional material should have a very limited effect on the activity and selectivity of the polyalkylene carbonate, and it is also necessary to facilitate the removal of the additional material after polymerization.

The present invention provides a method for efficiently producing a polyalkylene carbonate having a molecular weight controllability and a selectivity higher than a certain level.

The present invention includes a process for polymerizing carbon dioxide and an epoxide compound under a catalyst and a solvent, wherein the sum of the water content contained in the solvent, carbon dioxide, and epoxide compound in the reaction mixture before the initiation of the polymerization process is 10 to 1000 ppm Alkylene carbonate.

The weight average molecular weight of the resin prepared through the above polymerization conditions may be 10,000 to 1,000,000 g / mol.

The carbon dioxide may be continuously or discontinuously introduced at a molar ratio (carbon dioxide: epoxide compound molar ratio) of 1: 1 to 10: 1 based on the epoxide compound.

The catalyst is preferably a zinc-based catalyst, and the epoxide compound is an alkylene oxide having 2 to 20 carbon atoms, which is substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms; A cycloalkylene oxide having 4 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms; And styrene oxide having 8 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms.

The catalyst may be added in a molar ratio (catalyst: epoxide compound) of 1:50 to 1: 400 to the epoxide compound.

The solvent may be a chlorinated solvent, and preferred examples thereof include methylene chloride or ethylene dichloride.

The solvent may be methylene chloride or ethylene dichloride, and may be added at a weight ratio (solvent: epoxide compound weight ratio) of 0.1: 1 to 50: 1 to the epoxide compound.

The polymerization process may be carried out at 50 to 90 DEG C and 15 to 50 bar for 3 to 60 hours.

The present invention does not use a separate chain transfer agent (CTA) compound as known in the art and removes a separate molecular weight adjuster by adjusting the moisture content in the reaction mixture before the initiation of the polymerization process to the optimal range A polyalkylene carbonate having various molecular weights can be effectively produced without requiring a process.

FIG. 1 is a graph showing changes in molecular weight / selectivity by water content in a solvent except for reactants using a small polymerization reactor having a capacity of 2 L or less.
FIG. 2 is a graph showing changes in molecular weight / selectivity according to water content in a solvent excluding a reactant using a 1 m ³ large polymerization reactor.

Hereinafter, the present invention will be described in more detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

Also, " comprising "as used herein should be interpreted as specifying the presence of particular features, integers, steps, operations, elements and / or components, It does not exclude the presence or addition of an ingredient.

Hereinafter, a method for producing a polyalkylene carbonate having a molecular weight controlled by a water content in a polymerization reaction product according to a preferred embodiment of the present invention will be described in more detail.

According to one embodiment of the present invention, there is provided a process for producing a polyalkylene carbonate which adjusts the molecular weight by controlling the moisture content contained in the reaction mixture before the initiation of the polymerization process. Wherein the polyalkylene carbonate is prepared by polymerizing carbon dioxide and an epoxide compound under a catalyst and a solvent; The total amount of water contained in the solvent, carbon dioxide, and epoxide compound in the reaction mixture before the initiation of the polymerization process is 10 to 1000 ppm.

As described above, conventionally, in the production of the polyalkylene carbonate, various compounds were added to the polymer through a separate chain transfer agent (CTA) to control the molecular weight of the resulting polymer. However, Activity and selectivity of the reaction mixture, and a process of removing the molecular weight modifier compound added after polymerization has to be added, which causes a problem that the overall process efficiency is lowered.

Accordingly, in order to solve the problems of the prior art, it is not necessary to add a conventional molecular weight modifier compound to adjust the moisture content of the polymerization initiator to the optimum range before starting the polymerization reaction, thereby eliminating a separate molecular weight modifier A polyalkylene carbonate having various degrees of molecular weight and having a selectivity higher than a certain level.

In this method of the present invention, the total amount of water contained in the solvent, carbon dioxide, and epoxide compound in the reaction mixture before the initiation of the polymerization process is preferably within 15 ppm, preferably within 10 ppm, Is preferably controlled within 5 ppm. At this time, the raw material can be passed through a column packed with a molecular sieve. Since the molecular weight of the resin prepared through the solution polymerization is increased or decreased according to the water content contained in the reaction mixture before the initiation of the polymerization process, the distilled water is artificially introduced into the sufficiently purified reaction mixture before starting the polymerization process, It is desirable to appropriately adjust the target moisture content of the mixture. By adding distilled water in this way, it is possible to control the total amount of water contained in the solvent, carbon dioxide, and epoxide compound in the reaction mixture before the initiation of the polymerization process to 10 to 1000 ppm.

The molecular weight of the resin produced through such a polymerization process may preferably range from 10,000 g / mol to 1,000,000 g / mol. In addition, the selectivity of the resin produced through the above polymerization conditions can be 85% or more, preferably 90% or more.

In the present invention, the amount of water added for the above polymerization conditions has a very limited effect on the activity and selectivity of the polyalkylene carbonate, so that the water exhibits the same level of activity and selectivity in the polymerization using the sufficiently purified reaction mixture.

Here, the term "selectivity" refers to the content of the desired chemical reaction product in the overall chemical reaction product including the by-product produced through the polymerization reaction.

In the polymerization process, the selectivity refers to the content of the polyalkylene carbonate in the resultant chemical reaction product, and may exhibit a selectivity of about 85% or more.

The materials used in the solution polymerization will be described in more detail as follows.

The epoxide compound is an alkylene oxide having 2 to 20 carbon atoms which is substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms; A cycloalkylene oxide having 4 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms; And styrene oxide having 8 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms. More preferably, the epoxide compound may include an alkylene oxide having 2 to 20 carbon atoms which is substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms.

Specific examples of the epoxide compound include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, Epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-epoxy-7-octene, epifluorohydrin, epichlorohydrin, -Ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxy norbornene, limonene oxide, dieldrin , 2,3-epoxypropylbenzene, styrene oxide, phenylpropylene oxide, stilbene oxide, Propyl methoxy ether, chloropropyl methoxy ether, chloropropyl methoxy ether, chloropropyl methoxy ether, chlorostyrene benzoate, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyloxirane, glycidyl- Phenyl ether, biphenyl glycidyl ether, glycidyl naphthyl ether, and the like. Preferably, the epoxide compound uses ethylene oxide.

The solvent is preferably used in a weight ratio (solvent: epoxide compound weight ratio) of 0.1: 1 to 50: 1 to the epoxide compound, more preferably 0.5: 1 to 10: 1. The solvent may be methylene chloride or ethylene dichloride.

The carbon dioxide may be continuously or discontinuously introduced during the reaction but is preferably continuously introduced. In this case, it is preferable to use a continuous system or a semi-batch type polymerization reactor. If carbon dioxide is not continuously supplied, production of byproducts such as polyethylene glycol may increase separately from the carbonate copolymerization reaction aimed at in the present invention. The reaction pressure may be 5 to 50 bar or 10 to 40 bar when the carbon dioxide is continuously introduced into the polymerization.

In addition, the carbon dioxide may be introduced at a molar ratio (carbon dioxide: epoxide compound molar ratio) of 1: 1 to 10: 1 with respect to the epoxide compound. More preferably, the carbon dioxide may be introduced at a molar ratio of 1: 1 to 5: 1 relative to the epoxide compound. When carbon dioxide is introduced at the above-mentioned ratio, it is preferable that the polymerization reactor employs a continuous system or a semi-batch type system.

The catalyst used in the present invention can be carried out in the presence of a metal complex compound such as zinc, aluminum or cobalt, but a zinc-based catalyst is preferably used. The zinc-based catalyst is not limited in its kind and may include zinc complexes well known in the art.

In addition, the catalyst may be introduced at a molar ratio of epoxide compound: zeolite catalyst of 50: 1 to 400: 1. If the ratio is less than 50: 1, it may be difficult to exhibit sufficient catalytic activity in the solution polymerization. If the ratio is more than 400: 1, the residual monomer may remain excessively and the efficiency of the whole process may be deteriorated.

On the other hand, the method for producing the polyalkylene carbonate of the present invention is not particularly limited, but can be obtained, for example, by copolymerization of the above-mentioned alkylene oxide with carbon dioxide or by ring-opening polymerization of cyclic carbonate. The copolymerization of the alkylene oxide and carbon dioxide can be carried out in the presence of a metal complex compound such as zinc, aluminum or cobalt.

Accordingly, the polymerization step according to a preferred embodiment of the present invention is a step of supplying a catalyst, a solvent, an epoxide compound and carbon dioxide to a polymerization reactor, and then polymerizing a monomer containing an epoxide compound and carbon dioxide under a catalyst and a solvent . Further, such polymerization may be continuous polymerization.

After the solution polymerization is complete, a reaction mixture is formed which comprises a polyalkylene carbonate, unreacted residual monomer, catalyst residue, solvent and byproduct.

Further, the polymerization process can be carried out at 50 to 90 캜 and 15 to 50 bar for 3 to 60 hours. In addition, since the epoxide compound, especially ethylene oxide, has a self-polymerization temperature of 90, it may be more preferable to perform the solution polymerization at a temperature of 50 to 90 ° C in order to reduce the by-product content due to autopolymerization.

The polyalkylene carbonate of the present invention produced by this method may have a yield of 90% or more, and the molecular weight of the resin produced through the polymerization process may preferably be in the range of 10,000 g / mol to 1,000,000 g / mol. Preferable examples of the polyalkylene carbonate include polyethylene carbonate.

Hereinafter, preferred embodiments of the present invention will be described in detail. It should be understood, however, that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the present invention.

[ Example ]

Manufacturing example  1: Preparation of Organozinc Catalyst

In a 250 mL round bottom flask, 13.12 g (100 mmol) of glutaric acid in 150 mL toluene was dispersed under reflux and heated at 55 DEG C for 30 minutes.

Separately, 8.14 g (100 mmol) of ZnO was added to 150 mL of toluene and stirred to prepare a ZnO dispersion.

The ZnO dispersion was divided into quarters based on the volume, and 1/4 of the dispersion was first added to the glutaric acid solution to conduct the reaction. After one hour, another 1/4 of the ZnO dispersion was added to conduct the reaction. One hour later, another 1/4 of the ZnO dispersion was added to proceed the reaction. After 1 hour, the last 1/4 of the ZnO dispersion was added to proceed the reaction. The reaction mixture was heated at 55 ° C., heated to 110 ° C. and heated for 3 hours to remove water generated during the synthesis by using Dean Stark. After a white solid was formed, it was filtered, washed with acetone / ethanol and dried in a vacuum oven at 130 < 0 > C.

In this way, an organic zinc catalyst (Zn-based catalyst) was prepared.

Example  1: Molecular weight control experiment using small reactor

As the polymerization reactor, solution polymerization was carried out using an autoclave reactor (capacity: 30 mL to 2000 mL) equipped with a stirrer under the conditions shown in Table 1 below. First, the zinc dicarboxylate catalyst prepared in Preparation Example 1, methylene chloride (MC), ethylene oxide and carbon dioxide, which were prepared in Preparation Example 1, were fed into a reactor equipped with a stirrer, and solution polymerization was carried out under the conditions shown in Table 1 below. . At this time, the ethylene oxide, methylene chloride, and carbon dioxide were purified to maintain the water content below 15 ppm, and then the water content of the solvent was adjusted to 64 ppm by artificially introducing distilled water into the solvent (MC).

At this time, the polyalkylene carbonate produced had a weight average molecular weight of 348 kg / mol and showed a selectivity of 90%.

Example  2: Molecular weight control experiment using small reactor

Experiments were carried out in the same manner as in Example 1 by applying the conditions shown in Table 1 below.

At this time, the water content of the solvent (MC) was 132 ppm, and the weight average molecular weight of the polyalkylene carbonate produced was 172 kg / mol and showed a selectivity of 92%.

Comparative Example  1: Molecular weight control experiment using small reactor

The experiment was carried out in the same manner as in Example 1 by applying the conditions shown in Table 1 below, but the polymerization was carried out without artificially adding water to the reaction mixture after the purification of the monomer and the solvent. At this time, the water content in the solvent (MC) was 8 ppm, and the weight average molecular weight of the polyalkylene carbonate produced was 821 kg / mol and showed a selectivity of 92%.

Polymerization process conditions and reaction results according to Examples 1 to 2 and Comparative Example 1 are shown in Table 1 below.

Comparative Example 1 Example 1 Example 2 Catalyst (Cat.) Content (g) 0.4 0.4 0.4 Ethylene oxide (EO) content (g) 8.6 8.7 8.5 Methylene chloride (MC) content (g) 8.5 8.5 8.5 CO ₂ pressure (bar) 30 30 30 Polymerization process temperature (캜) 70 70 70 Moisture Content in Solvent (MC) (ppm) 8 64 132 Polymerization time (hr) 3 3 3 Molecular weight (M _w , kg / mol) 821 348 172 Selectivity (%) 92 90 92

As shown in Table 1, according to the present invention, it is possible to control the moisture content of the reactants without adding additional chain transfer agent in the polyalkylene carbonate polymerization, It was confirmed that the alkylene carbonate can be effectively produced and the selectivity of the same level as that of Comparative Example 1 in which water is not artificially introduced is exhibited.

Manufacturing example  2: Preparation of Organozinc Catalyst

In a 160 L sized reactor, 11.9 kg (89.3 mol) of glutaric acid were dispersed in 100 L of toluene under reflux and heated at 55 DEG C for 30 minutes.

Separately, 7.3 kg (90 mol) of ZnO was added to 30 L of toluene and stirred to prepare a ZnO dispersion.

The ZnO dispersion was divided into quarts based on the volume, and 1/4 of the ZnO dispersion was first added to the glutaric acid solution to conduct the reaction. After one hour, another 1/4 of the ZnO dispersion was added to conduct the reaction. One hour later, another 1/4 of the ZnO dispersion was added to proceed the reaction. After 1 hour, the ZnO dispersion was added to the final 1/4, and the reaction proceeded. The reaction mixture was allowed to react at 55 ° C, then heated to 110 ° C and heated for 3 hours to remove water generated during the synthesis by using Deanstock. After a white solid was formed, it was filtered, washed with acetone / ethanol and dried in a vacuum oven at 130 < 0 > C.

In this way, an organic zinc catalyst (Zn-based catalyst) was prepared.

Example  3: Depending on the moisture content Polyalkylene Carbonate  Molecular weight and selectivity change

Before the polymerization, carbon dioxide, ethylene oxide and methylene chloride (hereinafter referred to as CO ₂ , EO, and MC) were sufficiently purified using a molecular sieve. After that, the water content of MC was adjusted to 21 ppm to be used for the polymerization in order to control the molecular weight.

Then, an agitating flash drum and a twin-screw extruder for recovering the raw material feed tank, polymerization reactor and solvent, a biaxial extruder for removing by-products, an extruder for pelletizing, a centrifugal dryer and a pellet recovery device Was used in the production method of the resin composition.

First, an autoclave reactor equipped with a stirrer of 1 m ³ was used as the polymerization reactor. Then, the zinc-based catalyst obtained in Preparation Example 2, MC, EO, and CO ₂ were charged into a polymerization reactor via a raw material feed tank, and solution polymerization was carried out under the conditions shown in Table 2 below to prepare polyethylene carbonate.

After the solution polymerization was completed under the above conditions, unreacted carbon dioxide and ethylene oxide were removed through venting and sufficiently diluted, and most of the residual ethylene oxide was further removed using an RDC column. Thereafter, the catalyst was removed using an acid ion exchange resin, and the surface of the ion exchange resin was washed with water to recover glutaric acid as a catalyst raw material.

Thereafter, the number of revolutions of the main screw (Ø40) of the twin screw extruder (L / D = 60) was 30 rpm to 120 rpm, the temperature of the twelve screw zones was 40 to 180 degrees, MC was volatilized sequentially under the conditions of the drawing, and at the same time, extrusion with the die was carried out.

The extruded polyalkylene carbonate was pelletized to 2-5 mm size, dried thoroughly in a centrifugal dryer, and recovered through a pellet recovery device. At this time, the polyalkylene carbonate resin produced had a weight average molecular weight of 404 kg / mol and a selectivity of 95%.

Example  4: Depending on the moisture content Polyalkylene Carbonate  Molecular weight and selectivity change

Before the polymerization, CO ₂ , EO, and MC were sufficiently purified, and the polymerization was carried out by artificially adding distilled water to the MC so that the water content of MC was 68 ppm. The same production method as in Example 3 was used, and the amounts of the catalyst, CO ₂ , EO, and MC were as shown in Table 2 below.

At this time, the polyalkylene carbonate resin produced had a weight average molecular weight of 240 kg / mol and showed a selectivity of 93%.

Example  5: Depending on the moisture content Polyalkylene Carbonate  Molecular weight and selectivity change

Before the polymerization, CO ₂ , EO, and MC were sufficiently purified, and the polymerization was proceeded by artificially adding distilled water so that the water content of MC became 103 ppm. The same production method as in Example 3 was used, and the amounts of the catalyst, CO ₂ , EO, and MC were as shown in Table 2 below.

At this time, the polyalkylene carbonate resin produced had a weight average molecular weight of 192 kg / mol and showed a selectivity of 93%.

Example  6: Depending on the moisture content Polyalkylene Carbonate  Molecular weight and selectivity change

Before the polymerization, CO ₂ , EO, and MC were sufficiently purified, and the polymerization was proceeded by artificially adding distilled water so that the water content of MC was 129 ppm. The same production method as in Example 3 was used, and the amounts of the catalyst, CO ₂ , EO, and MC were as shown in Table 2 below.

At this time, the polyalkylene carbonate resin produced had a weight average molecular weight of 158 kg / mol and a selectivity of 93%.

Example  7: Depending on the moisture content Polyalkylene Carbonate  Molecular weight and selectivity change

Before the polymerization, CO ₂ , EO, and MC were sufficiently purified, and the polymerization was proceeded by artificially adding distilled water in an amount such that the water content of MC was 234 ppm. The same production method as in Example 3 was used, and the amounts of the catalyst, CO ₂ , EO, and MC were as shown in Table 2 below.

At this time, the polyalkylene carbonate resin produced had a weight average molecular weight of 135 kg / mol and a selectivity of 92%.

Comparative Example  2: Using a sufficiently purified water-containing reaction mixture Polyalkylene Of carbonate  Produce

After purification using a molecular sieve, the polymerization was carried out at a moisture content of 5 ppm of MC without addition of water.

The same production method as in Example 3-7 was used, and the amounts of the catalyst, CO ₂ , EO, and MC were as shown in Table 2 below.

At this time, the polyalkylene carbonate resin produced had a weight average molecular weight of 633 kg / mol and showed a selectivity of 95%.

Comparative Example  3: Depending on the ratio of the reaction mixture Polyalkylene Of carbonate  Molecular weight and selectivity change

After purification using a molecular sieve, the polymerization was carried out with the water content of MC of 7 ppm without addition of water.

The same production method as in Comparative Example 2 was used, and the amounts of the catalyst, CO ₂ , EO, and MC were as shown in Table 2 below.

At this time, the polyalkylene carbonate resin produced had a weight average molecular weight of 616 kg / mol and a selectivity of 92%.

Comparative Example  4: Polymerization temperature, pressure change Polyalkylene Of carbonate  Molecular weight and selectivity change

After purification using a molecular sieve, the polymerization was carried out at a moisture content of 5 ppm of MC without addition of water.

Using the same production method as in Comparative Example 2, polymerization pressure of 35 bar and polymerization temperature of 85 degrees were maintained in the polymerization reaction. The amounts of catalyst, CO ₂ , EO, and MC are shown in Table 2 below.

At this time, the polyalkylene carbonate resin produced had a weight average molecular weight of 660 kg / mol and a selectivity of 91%.

Polymerization conditions and polymerization results of the polyalkylene carbonate according to Examples 3 to 7 and Comparative Examples 2 to 4 are shown in Table 2 below.

Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 3 Example 4 Example 5 Example 6 Example 7 Catalyst (Cat.) Content (g) 3 1.5 3 3 3 4 3.5 4 Ethylene oxide (EO) content
(g) 67 101 67 100 67 100 240 240 Methylene chloride (MC)
Content (g) 325 300 330 300 330 300 240 240 CO ₂ content (kgr) 174 142 157 159 147 164 143 194 CO ₂ pressure (bar) 30 30 35 30 30 30 30 30 Polymerization process temperature (캜) 70 70 85 70 70 70 70 70 Moisture Content in Solvent (MC) (ppm) 5 7 5 21 68 103 129 234 Polymerization time (hr) 6 6 6 6 6 6 6 6 Molecular weight (M _w , kg / mol) 653 616 660 404 240 192 158 135 Selectivity (%) 95 92 91 95 93 93 93 92

As shown in Table 2, according to Examples 3 to 7 of the present invention, it is possible to control the moisture content of the reactants without additionally adding a separate chain transfer agent to the polyalkylene carbonate, It was confirmed that the polyalkylene carbonate of the present invention had the same degree of selectivity as that of Comparative Examples 2 to 4 in which water was not added artificially.

Claims (5)

Polymerizing the carbon dioxide and the epoxide compound in the presence of a catalyst and a solvent,
Wherein the total content of the water, the solvent, the carbon dioxide, and the water content contained in the reaction mixture before the initiation of the polymerization process is controlled to 10 to 1000 ppm to control the molecular weight of the polyalkylene carbonate.
The method according to claim 1,
Wherein the weight average molecular weight of the resin produced through the polymerization conditions is 10,000 to 1,000,000 g / mol.
The method according to claim 1,
Wherein the zinc-based catalyst is a zinc dicarboxylate-based catalyst prepared by reacting a zinc-based precursor with a dicarboxylic acid having 3 to 20 carbon atoms.
The method according to claim 1,
The epoxide compound is an alkylene oxide having 2 to 20 carbon atoms which is substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms; A cycloalkylene oxide having 4 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms; And styrene oxide having 8 to 20 carbon atoms which is substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms,
Wherein the solvent is a chlorinated solvent.
The method according to claim 1,
Wherein the molar ratio of catalyst: epoxide compound is from 1:50 to 1: 400, the molar ratio of carbon dioxide to epoxide compound is from 1: 1 to 10: 1, the weight ratio of solvent: epoxide compound is from 0.1: 1 to 50: 1,
Wherein the polymerization process is conducted at 50 to 90 and 15 to 50 bar for 3 to 60 hours.

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